Substituted tetrazolinones and their use as herbicides

ABSTRACT

Substituted tetrazolinones exhibit usefulness as herbicides and plant growth regulators.

This is a division of application Ser. No. 282,424 filed Dec. 9, 1988which is a division of application Ser. No. 860,712 now U.S. Pat. No.4,830,661, filed May 7, 1986, which is a continuation-in-art ofapplication Ser. No. 737,371 now U.S. Pat. No. 4,826,529 filed May 23,1985 which is a continuation-in-part of application Ser. No. 560,031filed Dec. 9, 1983 now U.S. Pat. No. 4,618,365.

BACKGROUND OF THE DISCLOSURE

1. Field of the Invention

The instant invention is directed to a new class of substitutedtetrazolinone compounds. More specifically, the instant inventionrelates to a new class of substituted tetrazolinone compounds which areuseful as herbicides and/or as plant growth regulators.

2. Background of the Prior Art

The synthesis of certain substituted tetrazolinones is known in the art.Thus, Horwitz, et al, JACS, 81 3076 (1959) and Tsuge et al, J. Org.Chem., 45 5130 (1980) provide methods for synthesizing tetrazolinones.These disclosures provide no utility for the classes of substitutedtetrazolinones synthesized.

The need for effective herbicides needs no special emphasis. The controlof weeds and undesirable vegetation is of great economic importancesince weed competition inhibits the production of foliage, fruit or seedof agricultural crops. The presence of weeds can reduce harvestingefficiency and the quality of the harvested crop. Weed control isessential for maximum production of many agronomic and horticulturalcrops including corn, (Zea mays L.), cotton (Gossypium SP), sunflower(Helianthus annus L.) and soybeans (Glycine max (L.) Merr.). Weeds onnoncropped areas may cause a fire hazard, undesirable drifting of sandor snow, and/or irritation to persons with allergies. Thus, suppressionof undesirable weed growth is very advantageous.

Moreover, the need for agricultural chemicals having significant effectson the growth and development of crop plant species is similarly wellknown. Thus, for many crops, it is highly desirable that certain plantgrowth regulatory effects by accomplished. In general, these growthregulatory effects include one or more of the following: dwarfing,cessation of terminal growth, inhibition or stimulation of axillary andintercalary growth, retardation or stimulation of internode elongation,inhibition or stimulation of flowering or reproductive development, andthe like.

SUMMARY OF THE INVENTION

It has now been found that a new class of substituted tetrazolinonesunexpectedly provides excellent herbicidal properties and plant growthregulatory effects.

In accordance with the instant invention, a compound having the formula:##STR1## wherein R is: C₁ -C₁₂ alkyl,

C₂ -C₁₃ alkoxyalkyl,

C₇ -C₉ aralkyl,

C₅ -C₆ cycloalkyl,

C₃ -C₁₂ alkenyl,

naphthyl,

phenyl,

phenyl substituted with at least one member selected from the groupconsisting of:

fluorine,

chlorine,

bromine,

iodine,

C₁ -C₄ alkyl,

C₁ -C₄ alkoxy,

methylenedioxy,

NR³ R⁴ wherein R³ and R⁴ are the same or different and are hydrogen orC₁ -C₆ alkyl,

C₂ -C₅ alkoxycarbonyl,

carboxy,

phenoxy,

nitro,

cyano,

trihalomethyl wherein halo is fluorine, chlorine or bromine,

trihalomethoxy wherein halo is fluorine, chlorine or bromine,

C₁ -C₆ alkylthio, and

C₁ -C₆ fluoroalkylthio; or benzyl substituted with at least one memberselected from the group consisting of:

fluorine,

chlorine,

bromine,

iodine,

C₁ -C₄ alkyl,

C₁ -C₄ alkoxy,

methylenedioxy,

C₂ -C₅ alkoxycarbonyl,

phenoxy,

nitro,

cyano,

trihalomethyl wherein halo is fluorine, chlorine or bromine,

trihalomethoxy wherein halo is fluorine, chlorine or bromine,

C₁ -C₆ alkylthio, and

C₁ -C₆ fluoroalkylthio;

R¹ is selected from the group consisting of:

C₁ -C₆ alkyl,

C₃ -C₆ alkenyl,

C₅ -C₆ cycloalkyl,

C₇ -C₉ aralkyl,

C₇ -C₉ aralkyl substituted with at least one member selected from thegroup consisting of:

fluorine,

chlorine,

bromine,

iodine,

C₁ -C₆ alkyl,

C₁ -C₂ haloalkyl wherein halo is fluorine, chlorine or bromine,

halomethoxy wherein halo is fluorine, chlorine or bromine,

C₁ -C₆ alkoxy,

C₁ -C₆ alkylthio,

C₁ -C₆ fluoroalkylthio,

phenoxy,

phenylthio,

carboxy,

C₂ -C₅ alkoxycarbonyl,

nitro,

cyano, and

NR⁷ R⁸ wherein R⁷ and R⁸ are the same or different and are hydrogen, C₁-C₆ alkyl, C₄ -C₈ alkylene or C₄ -C₈ oxydialkylene; or

naphthyl,

phenyl, and

phenyl substituted with at least one member selected from the groupconsisting of:

fluorine,

chlorine,

bromine,

iodine,

C₁ -C₆ alkyl,

C₁ -C₂ haloalkyl wherein halo is fluorine, chlorine or bromine:

halomethoxy wherein halo is fluorine, chlorine or bromine,

C₁ -C₆ alkoxy,

C₁ -C₆ alkylthio,

C₁ -C₆ fluoroalkylthio,

phenoxy,

phenyl,

phenylthio,

carboxy,

C₂ -C₅ alkoxycarbonyl,

nitro,

cyano, and

NR⁷ R⁸ wherein R⁷ and R⁸ are the same or different and are hydrogen, C₁-C₆ alkyl, C₄ -C₈ alkylene or C₄ -C₈ oxydialkylene: and

R² is a radical having the formula: ##STR2## wherein X is oxygen or CH₂,and Z is --CH₂ --CH₂ or --CR⁹ R¹⁰ -- wherein R⁹ and R¹⁰ are the same ordifferent and are hydrogen or methyl,

is disclosed.

In further accordance with the instant invention a composition isprovided comprising the compound of this invention with a carrier.

In still further accordance with the present invention a method forcontrolling weeds and undesirable vegetation employing the compositionof this invention is taught.

In yet further accordance with the present invention, a method forregulating the growth of plants employing the composition of thisinvention is taught.

DETAILED DESCRIPTION

The present invention is directed to a compound having the structuralformula: ##STR3## wherein R is: C₁ -C₁₂ alkyl,

C₂ -C₁₃ alkoxyalkyl,

C₇ -C₉ aralkyl,

C₅ -C₆ cycloalkyl,

C₃ -C₁₂ alkenyl,

naphthyl,

phenyl,

phenyl substituted with at least one member selected from the groupconsisting of:

fluorine,

chlorine,

bromine,

iodine,

C₁ -C₄ alkyl,

C₁ -C₄ alkoxy,

methylenedioxy,

NR³ R⁴ wherein R³ and R⁴ are the same or different and are hydrogen orC₁ -C₆ alkyl,

C₂ -C₅ alkoxycarbonyl,

carboxy,

phenoxy,

nitro,

cyano,

trihalomethyl wherein halo is fluorine, chlorine or bromine,

trihalomethoxy wherein halo is fluorine, chlorine or bromine,

C₁ -C₆ alkylthio, and

C₁ -C₆ fluoroalkylthio; or

benzyl substituted with at least one member selected from the groupconsisting of:

fluorine,

chlorine,

bromine,

iodine,

C₁ -C₄ alkyl,

C₁ -C₄ alkoxy,

methylenedioxy,

C₂ -C₅ alkoxycarbonyl,

phenoxy,

nitro,

cyano,

trihalomethyl wherein halo is fluorine, chlorine or bromine,

trihalomethoxy wherein halo is fluorine, chlorine or bromine,

C₁ -C₆ alkylthio, and

C₁ -C₆ fluoroalkylthio;

R¹ is selected from the group consisting of:

C₁ -C₆ alkyl,

C₃ -C₆ alkenyl,

C₅ -C₆ cycloalkyl,

C₇ -C₉ aralkyl,

C₇ -C₉ aralkyl substituted with at least one member selected from thegroup consisting of:

fluorine,

chlorine,

bromine,

iodine,

C₁ -C₆ alkyl,

C₁ -C₂ haloalkyl wherein halo is fluorine, chlorine or bromine;

halomethoxy wherein halo is fluorine, chlorine or bromine,

C₁ -C₆ alkoxy,

C₁ -C₆ alkylthio,

C₁ -C₆ fluoroalkylthio,

phenoxy,

phenylthio,

carboxy,

C₂ -C₅ alkoxycarbonyl,

nitro,

cyano, and

NR⁷ R⁸ wherein R⁷ and R⁸ are the same or different and are hydrogen, C₁-C₆ alkyl, C₄ -C₈ alkylene or C₄ -C₈ oxydialkylene;

naphthyl,

phenyl, and

phenyl substituted with at least one member selected from the groupconsisting of:

fluorine,

chlorine,

bromine,

iodine,

C₁ -C₆ alkyl,

C₁ -C₂ haloalkyl wherein halo is fluorine, chlorine or bromine;

halomethoxy wherein halo is fluorine, chlorine or bromine,

C₁ -C₆ alkoxy,

C₁ -C₆ alkylthio,

C₁ -C₆ fluoroalkylthio,

phenoxy,

phenyl,

phenylthio,

carboxy,

C₂ -C₅ alkoxycarbonyl,

nitro,

cyano, and

NR⁷ R⁸ wherein R⁷ and R⁸ are the same or different and are hydrogen, C₁-C₆ alkyl, C₄ -C₈ alkylene or C₄ -C₈ oxydialkylene; and

R² is a radical having the formula: ##STR4## wherein X is oxygen or CH₂,and Z is --CH₂ --CH₂ or --CR⁹ R¹⁰ -- wherein R⁹ and R¹⁰ are the same ordifferent and are hydrogen or methyl.

Among the more preferred compounds of this invention are those wherein:

R is C₁ -C₄ alkyl,

phenyl, or

phenyl substituted with at least one member of the group consisting of:

C₁ -C₃ alkyl and

C₁ -C₃ alkoxy:

R₁ is C₁ -C₄ alkyl: and

R₂ is 3,4-methylenedioxyphenyl.

The compounds of this invention are prepared by reacting a tetrazolinonecompound having the formula: ##STR5## wherein M is hydrogen or alkalimetal (such as Li, Na or K) and R is as defined above with a carbamoylhalide having the formula QCONR¹ R², wherein Q is chlorine or bromineand R¹ and R² have the meanings above.

When M is hydrogen, the reaction is preferably conducted in the presenceof a suitable acid acceptor such as pyridine or a tertiary amine (e.g.,triethylamine). It is noted that this tetrazolinone compound may besynthesized by the methods disclosed in the Horwitz et al and Tsuge etal references mentioned above. The equivalent ratio of Q/M (asrepresentative of the above reactants) may vary from about 0.75/1 toabout 2/1, preferably from about 0.9/1 to about 1.5/1. Excess of M maybe advantageous in the purification of product since the M-typetetrazolinone is soluble in base. The reaction temperature may rangefrom about 40° C. to the boiling point of the solvent used. Typically,the reaction is conducted under reflux conditions. Suitable solvents arethose which are inert to the reactant, such as acetone, acetonitrile,toluene, chloroform and the like. The reaction time may vary fromseveral minutes or less to several hours or more depending on factorssuch as reaction batch size, reaction temperature, and the like.

Alternatively, the compounds of this invention may be prepared byreacting a tetrazolinone having the formula [I] above with phosgene, andthen further reacting the product of such reaction with the appropriatesecondary amine.

The instant invention is also directed to a composition comprising thesubstituted tetrazolinone compound of this invention and a carriertherefor. The carrier employed in one preferred embodiment of thisinvention is a finely-divided or granular inorganic or organic materialsuch as attapulgite clay, sand, vermiculite, ground corn cobs, activatedcarbon and the like. The compound of this invention may be impregnatedon the finely-divided or granular material.

The carrier may also be an inert powder. Preferably, the inert powder isone of the mineral silicates, e.g., mica, talc, pyrophyllite and clays.In this case, the composition is formed by grinding the compound of thisinvention into a fine powder and mixing it with the inert powder towhich a surface active dispersing agent has been added.

A third carrier is the combination of the above inert powder and water.This carrier employs the wettable powder dispersed in water.

Yet another carrier is a solvent and water. In this embodiment thecompound of this invention is dissolved in a solvent such as benzene,toluene or other aliphatic or aromatic hydrocarbon. An emulsifiableconcentrate is formed with the addition of a surface active and/ordispersing agent. The emulsifiable concentrate is then dispersed inwater. In this composition water solubility may be increased using acosolvent system involving acetone, dimethyl sulfoxide or other watermiscible solvent.

It is noted that the surface active agents preferred for use in thecomposition of this invention are well known to those skilled in theart. In addition, suitable surface active agents for use in thecomposition of this invention are provided in McCutcheon's Detergentsand Emulsifiers, 1970, Allured Publishing Corp., Ridgewood, N.J.: U.S.Pat. No. 2,614,916, columns 2 to 4; and U.S. Pat. No. 2,547,727, columns3 and 4.

The present invention is furthermore directed to a method of controllingweeds by application of a herbicidally effective amount of thecomposition of this invention.

In the case where the composition comprises impregnated granules of thecompound of this invention, application, to control weeds, is byspreading on the soil. The wettable powder may be similarly applied. Inthe case where the wettable powder is dispersed in water, thiscomposition controls weeds by spraying the dispersion onto the soilsurface. Where an emulsion is formed that emulsion is likewise sprayedonto the soil surface.

When employed as a herbicide, the concentration of the compound of thisinvention in the composition of this invention may vary widely, e.g.from 1 to 95%. The concentration of active compound in dispersionsapplied to the soil or foliage is generally from 0.002% to about 75%.

For use as a pre-emergence herbicide the compound of this invention istypically applied at rates of from about 0.05 to about 25 pounds peracre (from about 0.056 to about 28 kg/ha) to soil which contains weedand crop seed, namely either to the surface of the soil or incorporatedinto the upper one to three inches (2.5 to 7.5 cm.) of soil. Thecompound may be employed singly or as a mixture of two or morechemicals.

When employed as a herbicide, the most suitable rate of application inany given case will depend on such factors as soil type, soil pH, soilorganic matter content, the quantity and intensity of rainfall beforeand after treatment, the air and soil temperature, light intensity andlight duration per day. All of these factors can have an influence onthe efficacy of the chemicals for a given weed control use.

The herbicide use may include control of vegetation at industrial sitesor selective weed control in crop fields.

In addition, the present invention is directed to a method of regulatingthe growth of plants by the application of a plant growth regulatoryeffective amount of the composition of this invention. It will beunderstood that the term plant, as used herein, includes plant partssuch as foliage, roots, flower stems and seeds. Depending on the cropvariety, dosage, time of application and certain cultural practices, thegrowth regulating effects which may be obtained include one or more ofthe following: dwarfing, cessation of terminal growth, inhibition ofaxillary and intercalary growth, retardation of internode elongation,inhibition of flowering or reproductive development, and the like.

Compounds of this invention may be used alone, or in combination withone or more pesticidal compositions, or in combination with one or morespray adjuvants (e.g. surface active agents, stickers, spreaders,emulsifiers, suspending agents, or extenders). The amount of activecompound employed follows conventional practice for plant growthregulatory uses, and the chemicals are suitable applied as a formulationin accordance with conventional agricultural chemical practice.

The most suitable dosage of application of the active ingredient(s) forplant growth regulatory effects and the type and amount of adjuvantsubstances to be added to the spray solution will depend on a number offactors, including the plant species: the stage of plant development;the mode of application: the specific biological effect desired: the airand soil temperature: the quantity and intensity of rainfall before andafter treatment; the soil type, pH, fertility and moisture and organicmatter content; the physiological condition and vigor of the targetplants; the relative humidity and wind velocity of the air around thecrop; the extent and density of the foliar canopy of the target plant;the light quality, intensity and duration each day: the type andinterval of previous and subsequent crop protectant chemicalapplications. All of these factors may have an influence on the efficacyof chemicals applied as plant growth regulators. However, one skilled inthe art can, by routine experimentation, readily determine optimumconditions for the employment of any particular compound of thisinvention.

EXAMPLES

The following examples are given to illustrate the invention. Sincethese examples are illustrative of the invention, the invention shouldnot be deemed to be limited thereto.

EXAMPLE 1 Preparation of 1-Ethyl-5(4H)tetrazolinone-4-carbonyl Chloride

A 23.3% phosgene solution in toluene (85.0 grams, 0.20 mole) was furtherdiluted with 100 ml. of toluene and the solution was cooled to 10° C. Asolution of 18.2 grams (0.16 mole) of 1-ethyl-5(4H)tetrazolinone, 23.3ml. (17.0 grams, 0.168 mole) of triethylamine, 0.20 gram (0.0016 mole)of 4-dimethylaminopyridine and 70 ml. of toluene was added to thephosgene solution over a period of about 10 minutes keeping the reactiontemperature below 28° C. The mixture was stirred for 0.5 hour andfiltered to remove the precipitated salt. The filtrate was evaporated todryness and finally warmed to 40° C. (0.2 mm) giving 20.5 grams of anoily solid. Recrystallization from toluene/hexane yielded 15.4 grams(55%) of a light-tan granular solid, m.p. 71°-76° C. The structure wasconfirmed by IR.

EXAMPLE 2 Preparation of1-Ethyl-4-[N-(2-propyl)-N-(3,4-methylenedioxyphenyl)carbamyl]-5(4H)tetrazolinone(Compound No. 1)

1-ethyl-5(4H)tetrazolinone-4-carbonyl chloride (2.65 grams, 0.015 mole),2.0 ml. of pyridine and 2.5 grams (0.014 mole) ofN-(2-propyl)-3,4-methylenedioxyaniline were combined whereupon a slightexothermic reaction occurred. The reaction mixture was stirred forsixteen hours. The pyridine hydrochloride and the product precipitatedfrom the mixture. Water was added to remove the salt, and the insolubleproduct was removed by filtration. Recrystallization from ethanolyielded 2.3 grams (52%) of white crystals, m.p. 93°-94° C.

The structure shown in Table I was confirmed by IR and NMR spectra.

                  TABLE I                                                         ______________________________________                                         ##STR6##                                                                     Cpd. No.   R        R.sup.1     X   Z                                         ______________________________________                                        1          CH.sub.3 CH.sub.2                                                                      i-C.sub.3 H.sub.7                                                                         O   CH.sub.2                                  ______________________________________                                    

Following essentially the procedures outlined above additional compoundswithin the scope of this invention are prepared. These compounds,compounds 2-8, are defined in Table II.

                  TABLE II                                                        ______________________________________                                        Cpd. No. R        R.sup.1   X    Z                                            ______________________________________                                        2        CH.sub.3 i-C.sub.3 H.sub.7                                                                       O    CH.sub.2                                     3        C.sub.6 H.sub.5                                                                        i-C.sub.3 H.sub.7                                                                       O    CH.sub.2                                     4        CH.sub.3 CH.sub.2                                                                      CH.sub.3  O    CH.sub.2                                     5        CH.sub.3 CH.sub.2                                                                      2-butyl   O    CH.sub.2                                     6        CH.sub.3 i-C.sub.3 H.sub.7                                                                       CH.sub.2                                                                           CH.sub.2                                     7        CH.sub.3 i-C.sub.3 H.sub.7                                                                       CH.sub.2                                                                           CH.sub.2 CH.sub.2                            8        CH.sub.3 i-C.sub.3 H.sub.7                                                                       CH.sub.2                                                                            ##STR7##                                    ______________________________________                                    

EXAMPLE 4

To illustrate the effectiveness of the previously described substitutedtetrazolinones of this invention as pre-emergence herbicide, 300 mg ofcompound 1 was dissolved in a composition comprising 10 ml acetone towhich 30 mg emulsifying agent, ethoxylated sorbitan monolaurate, wasadded. The solution was diluted to 100 ml with distilled water. Tenmilliliters of this 3000 ppm solution was diluted to 250 ppm withdistilled water. The chemical was applied at the rate of 10 pounds/acre(11.2 kg/ha) by drenching 46 ml of the 250 ppm solution on the surfaceof soil in 41/2 inch (11.25 cm) plastic pots wherein seeds of thefollowing weeds had been planted: velvetleaf (Abutilon theophrastimedic) (VL), jimsonweed (Datura stramonium L.) (JW), tall morning glory(Ipomea purpurea L. Roth) (TM), switchgrass (Panicum virgatum L.) (SG),barnyardgrass (Echinochloa crusgalli (L.) Beauv.) (BG), green foxtail(Setria viridis (L.), Beauv.) (GF). The percent control of the weedscompared to untreated checks was determined two weeks after treatment.TABLE III summarizes the results achieved with compounds formulated asindicated above, and the data clearly indicate the good to excellentherbicidal efficacy of compounds of this invention.

                  TABLE III                                                       ______________________________________                                        Preemergence Activity                                                         (Percent Control at 11.2 kg/ha)                                               Cpd. No. VL       JW     TM     BG   SG     GF                                ______________________________________                                        1        80       60     100    100  100    100                               ______________________________________                                    

Similar herbicidal results are achieved with Compound Numbers 2-8 whenapplied to weeds in a manner indicated in Example 4.

EXAMPLE 5 Retardation of Plant Growth

To illustrate the effectiveness of the described compounds as plantgrowth regulants, 600 mg of chemical were dissolved in a 10 ml organicsolvent comprising acetone to which 30 mg of an emulsifying agent,"Tween 20" (trademark) (an ethoxylated sorbitan monolaurate), was added.This solution was diluted to 200 ml with distilled water, producing a3000 ppm solution/suspension. By appropriate dilutions with distilledwater, 1000 and 500 ppm solution/suspensions were prepared. The spraysolution/suspensions were atomized with a DeVilbiss (trademark) No. 152sprayer and wetted the foliage to the drip point of soybean plants(Glycine max (L.) Merr., cv. Williams, 2 weeks old), cotton plants(Gossypium hirsutum L. cv. Stoneville 213, 3-4 weeks old), bean plants(Phaseolus vulgaris L. cv. Pinto III, 2 weeks old), barley plants(Hordeum vulgare L. cv. Herta, 1 week old) and rice plants (Oryza sativaL. cv. Nato, 1 week old). After 1 to 3 weeks (depending on plantspecies) in a greenhouse, the plants were evaluated for retardation ofvegetative growth. A summary of growth retardation data appears in TableIV.

                  TABLE IV                                                        ______________________________________                                        Percent Plant Growth Retardation                                              Cpd.  Barley   Bean      Cotton Soybean Rice                                  No.   3000 ppm 1000 ppm  3000 ppm                                                                             3000 ppm                                                                              1000 ppm                              ______________________________________                                        1     50       100       --*    100     --*                                   ______________________________________                                         *--Indicates not tested                                                  

The above embodiments and examples illustrate the scope and spirit ofthe instant invention. These embodiments and examples will make apparentto those skilled in the art, other embodiments and examples within thescope of the present invention. Therefore, the instant invention shouldbe limited only by the appended claims.

What is claimed:
 1. A method for controlling weeds by applying to thelocus where the control of weeds is desired a herbicidally effectiveamount of a compound having the formula: ##STR8## wherein R is: C₁ -C₄alkyl,phenyl, or phenyl substituted with at least one member of thegroup consisting of:C₁ -C₃ alkyl and C₁ -C₃ alkoxy; R¹ is C₁ -C₄ alkyl;and R² is a radical having the formula: ##STR9## wherein X is oxygen orCH₂, and Z is --CH₂ --CH₂ or --CR⁹ R¹⁰ -- wherein R⁹ and R¹⁰ are thesame or different and are hydrogen or methyl.
 2. A method in accordancewith claim 1 wherein said weeds are controlled by applying said compoundto the soil prior to the emergence of said weeds.